Dinuclear platinum(II) sulfide–thiolate complexes [Pt2(μ-S)(μ-SR)(PPh3)4]+ containing fluorinated substituents and the identification of a S⋯C6F5 π interaction in the crystal structure of [Pt2(μ-S)(μ-SCH2C6F5)(PPh3)4]BPh4·2C6H6

Henderson, William; Saunders, Graham C.; Hor, T. S. Andy

doi:10.1016/j.ica.2010.12.020

Cited by 11 publications

(2 citation statements)

References 31 publications

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“…In some cases it may be possible to obtain thiolate ligands not easily accessible by other methodologies. This methodology has been employed in the synthesis of thiolate ligands containing, for example, fluorinated substituents, 16 or semicarbazone, urea, oxime and other groups. 17 The use of a dialkylating agent allows extension of the methodology to generate complexes containing a dithiolate ligand, 18 and the catalytic potential of this methodology for the synthesis of organosulfur compounds has been commented upon.…”

Section: Introductionmentioning

confidence: 99%

A novel structural rearrangement reaction of dialkylated derivatives of [Pt2(μ-S)2(PPh3)4] involving Pt–C bond formation

et al. 2012

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Reaction of [Pt(2)(μ-S)(2)(PPh(3))(4)] with the dialkylating agents ClCH(2)C(O)CH(2)Cl or ClCH(2)C(=NNHC(O)NH(2))CH(2)Cl gives the dicationic di-μ-thiolate complexes [Pt(2){μ-SCH(2)C(O)CH(2)S)(PPh(3))(4)](2+) or [Pt(2){μ-SCH(2)C(=NNHC(O)NH(2))CH(2)S}(PPh(3))(4)](2+), isolated as BPh(4)(-) salts and characterised by ESI mass spectrometry, NMR spectroscopy and single-crystal X-ray crystallography. Treatment of the complex [Pt(2){μ-SCH(2)C(O)CH(2)S)(PPh(3))(4)](2+), which contains a [6.6.4] bicyclic system, with hydroxide ions results in deprotonation of a CH(2) group and rearrangement of the resulting monocation, giving [Pt(2)(μ-SCH(2)C(O)CHS}(PPh(3))(4)](+), isolated as its PF(6)(-) salt. An X-ray structure determination shows the complex to have a novel rearranged [6.5.5] bicyclic system containing a Pt-S-Pt-S-C five-membered ring with a Pt-C bond. The alkyl ligand has a high trans-influence, manifest in a long trans Pt-P bond and small (1)J(PtP) coupling constant to the trans PPh(3) ligand. Reaction of [Pt(2)(μ-S)(2)(PPh(3))(4)] with the 2,4-dinitrophenylhydrazone derivative of 1,3-dichloroacetone leads to the closely related complex [Pt(2){μ-SCH(2)C(=NNHAr)CHS}(PPh(3))(3)Cl] [Ar = C(6)H(3)(NO(2))(2)] in which a PPh(3) ligand is substituted by a chloride.

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Section: Introductionmentioning

confidence: 99%

A novel structural rearrangement reaction of dialkylated derivatives of [Pt2(μ-S)2(PPh3)4] involving Pt–C bond formation

et al. 2012

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“…Since the early discoveries of the nucleophilic nature of the platinum(II) sulfide complex [Pt 2 (-S) 2 (PPh 3 ) 4 ] 1 [1,2,3,4] there have been extensive studies into the chemistry of this versatile complex and analogous complexes with {Pt 2 S 2 }, [5,6,7] [9,10] cores. There is particular interest in the alkylation [11,12,13,14,15,16] and arylation [17,18] chemistry of {Pt 2 S 2 } complexes, and the alkylation of {Pt 2 Se 2 } complexes, [19,20] because of the significant potential to synthesise novel thiolate (or selenolate) complexes using suitable organic electrophiles. The products formed with organic electrophiles are very much dependent on the nature of the electrophile.…”

Section: Introductionmentioning

confidence: 99%

Further studies on the dialkylation chemistry of [Pt2(μ-S)2(PPh3)4] with activated alkyl halides RC(O)CH2X (X=Cl, Br)

Ujam

Henderson

Nicholson

et al. 2011

Inorganica Chimica Acta

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Further studies have been carried out into the reactivity of [Pt 2 (-S) 2 (PPh 3) 4 ] towards a range of activated alkylating agents of the type RC(O)CH 2 X (R = organic moiety e.g. phenyl, pyrenyl; X = Cl, Br). Alkylation of both sulfide centres is observed for PhC(O)CH 2 Br, 3-(bromoacetyl)coumarin [CouC(O)CH 2 Br], and 1-(bromoacetyl)pyrene [PyrC(O)CH 2 Br], giving dications [Pt 2 {-SCH 2 C(O)R} 2 (PPh 3) 4 ] 2+ , isolated as their PF 6 salts. The X-ray structure of [Pt 2 {-SCH 2 C(O)Ph} 2 (PPh 3) 4 ](PF 6) 2 shows the presence of short Pt•••O contacts. In contrast, the corresponding chloro compounds [typified by PhC(O)CH 2 Cl] and imino analogues [e.g. PhC(NOH)CH 2 Br] do not dialkylate [Pt 2 (-S) 2 (PPh 3) 4 ]. The ability of PhC(O)CH 2 Br to dialkylate [Pt 2 (-S) 2 (PPh 3) 4 ] allows the synthesis of new mixed-alkyl dithiolate derivatives of the type [Pt 2 {-SCH 2 C(O)Ph}(-SR)(PPh 3) 4 ] 2+ (R = Et or n-Bu), through alkylation of in situ-generated monoalkylated compounds [Pt 2 (-S)(-SR)(PPh 3) 4 ] + (from [Pt 2 (-S) 2 (PPh 3) 4 ] and excess RBr). In these heterodialkylated systems ligand replacement of PPh 3 occurs by the bromide ions in the reaction mixture forming monocations [Pt 2 {-SCH 2 C(O)Ph}(-SR)(PPh 3) 3 Br] +. This ligand substitution can be easily suppressed by addition of PPh 3 to the reaction mixture. The complex [Pt 2 {-SCH 2 C(O)Ph}(-SBu)(PPh 3) 4 ] 2+ was crystallographically characterised. X-ray crystal structures of the bromide-containing complexes [Pt 2 {-SCH 2 C(O)Ph}(-SR)(PPh 3) 3 Br] + (R = Et, Bu) are also reported. In both structures the coordinated bromide is trans to the SCH 2 C(O)Ph ligand, which adopts an axial position, while the ethyl and butyl substituents adopt equatorial positions, in contrast to the structures of the dialkylated complexes [Pt 2 {-SCH 2 C(O)Ph} 2 (PPh 3) 4 ] 2+ and [Pt 2 {-SCH 2 C(O)Ph}(-SBu)(PPh 3) 4 ] 2+ (and many other known analogues) where both alkyl groups adopt axial positions.

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Using electrospray ionisation mass spectrometry as a synthesis-targeting technique – An update on the chemistry of the platinum chalcogenide dimers [Pt2(μ2-E)2(PPh3)4] (E=S, Se)

Henderson¹,

Hor²

2014

Inorganica Chimica Acta

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Dinuclear platinum(II) sulfide–thiolate complexes [Pt2(μ-S)(μ-SR)(PPh3)4]+ containing fluorinated substituents and the identification of a S⋯C6F5 π interaction in the crystal structure of [Pt2(μ-S)(μ-SCH2C6F5)(PPh3)4]BPh4·2C6H6

Cited by 11 publications

References 31 publications

A novel structural rearrangement reaction of dialkylated derivatives of [Pt2(μ-S)2(PPh3)4] involving Pt–C bond formation

A novel structural rearrangement reaction of dialkylated derivatives of [Pt2(μ-S)2(PPh3)4] involving Pt–C bond formation

Further studies on the dialkylation chemistry of [Pt2(μ-S)2(PPh3)4] with activated alkyl halides RC(O)CH2X (X=Cl, Br)

Using electrospray ionisation mass spectrometry as a synthesis-targeting technique – An update on the chemistry of the platinum chalcogenide dimers [Pt2(μ2-E)2(PPh3)4] (E=S, Se)

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